JP5306183B2 - High density polyethylene composition, method of making the same, product made therefrom, and method of making such product - Google Patents

Abstract

The instant invention is a high-density polyethylene composition, method of producing the same, articles made therefrom, and method of making such articles. The high-density polyethylene composition of the instant invention includes a first component, and a second component. The first component is a high molecular weight ethylene alpha-olefin copolymer having a density in the range of 0.915 to 0.940 g/cm3, and a melt index (I21.6) in the range of 0.5 to 10 g/10 minutes. The second component is a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g/cm3, and a melt index (I2) in the range of 50 to 1500 g/10 minutes. The high-density polyethylene composition has a melt index (I2) of at least 1, a density in the range of 0.950 to 0.960 g/cm3, and g' of 1.

Description

  The present invention relates to high density polyethylene compositions, methods of making the same, and products made therefrom.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a non-provisional application claiming priority from US patent application Ser. No. 60 / 796,809, filed May 2, 2006, entitled “High Density Polyethylene Composition and Method of Making The Same” The teachings of which are fully reproduced below in this specification.

Background of the Invention The use of polymeric materials to produce molded articles such as closure devices and containers is generally known. Various methods can be used to manufacture closure devices such as bottle caps or containers such as bottles. For example, such closure devices can be manufactured by compression molding or injection molding processes; alternatively, the container can be manufactured by blow molding, injection blow molding, or injection stretch blow molding.

  In the compression molding process, a two-piece mold provides a cavity in the shape of the desired molded part. Heat the mold. Fill the lower half of the mold with the appropriate amount of melt molding material from the extruder. Two mold parts are brought together under pressure. The molding material softened by heat is thereby welded to a continuous mass having the same shape as the cavity. If the molding material is a thermosetting material, the continuous mass can be hardened by further heating in the mold under pressure. If the molding material is a thermoplastic material, the continuous mass can be hardened by cooling in the mold under pressure.

  In the injection molding process, the molding material is fed to the extruder via a hopper. The extruder conveys the molding material, heats it, melts it and presses it to form a melt stream. The melt stream is forced out of the extruder through a nozzle and into a relatively cool mold that is kept closed under pressure, thereby filling the mold. The melt cools and hardens and hardens completely. Next, the mold is opened and the molded part is taken out.

  In a blow molding process, such as injection blow molding, the molding material is melted and then formed into a tube or parison. The end of the tube or parison is sealed except to the extent that blown air can enter. A sealed tube or parison is inflated inside the mold, thereby taking the shape of the mold. The molded article is cooled and then discharged from the mold. If necessary, the molded article is then deburred.

  In general, closure devices, such as soda bottle caps, should be strong enough to withstand the pressure of carbonated beverages, and must be soft enough to give the bottle a good seal without the need for an inner liner. Don't be. In addition, closure devices such as soda bottle caps generally provide good environmental stress crack resistance, good impact strength, good removal torque, and good strip torque. Should have. Various techniques have been used to provide such a closure device with acceptable characteristics.

  For example, it is also generally well known to use polypropylene polymers as bottle cap closures that have an inner liner made of soft ethylene / vinyl acetate (EVA), polyvinyl chloride (PVC), butyl rubber, etc. for the required strength. However, this two-part structure is expensive because it requires an inner liner. Furthermore, it is more convenient and convenient to use a one-piece closure that does not include a liner.

  In an attempt to eliminate the need for a two-part structure, the use of various blends of polymers has been proposed. However, acceptable properties such as not requiring a liner to promote sealing, acceptable flavor and odor, satisfactory stress crack resistance, and cap impact strength to prevent cap failure, etc. There is still a need for a polymer blend that can be molded into a closure device having.

SUMMARY OF THE INVENTION The present invention is a high density polyethylene composition, a method of making it, a product made therefrom, and a method of making such a product. The high-density polyethylene composition of the present invention includes a first component and a second component. The first component is a high molecular weight ethylene α-olefin copolymer having a density in the range of 0.915 to 0.940 g / cm ³ and a melt index (I _21.6 ) in the range of 0.5 to 10 g / 10 minutes. It is. The second component is a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g / cm ³ and a melt index (I ₂ ) in the range of 50 to 1500 g / 10 minutes. The high density polyethylene composition has a melt index (I ₂ ) of at least 1, a density in the range of 0.950 to 0.960 g / cm ³ , and one or more g ′. The method for producing a high density polyethylene composition includes the following steps. (1) introducing ethylene and one or more α-olefin comonomers into the first reactor; (2) ethylene in the presence of one or more α-olefin comonomers in the first reactor. (Co) polymerization, thereby producing a first component (the first component has a density in the range of 0.915 to 0.940 g / cm ³ , and in the range of 0.5 to 10 g / 10 min. A high molecular weight ethylene α-olefin copolymer having a melt index (I _21.6 ); (3) introducing a first component and further ethylene into a second reactor; (4) a second reactor. Polymerizing further ethylene therein, thereby producing a second component (the second component has a density in the range of 0.965 to 0.980 g / cm ³ , and a mel in the range of 50 to 1500 g / 10 min. Doo index (I ₂₎ is a low molecular weight ethylene polymer having a); and (5) thereby stage of producing a high-density polyethylene composition (high-density polyethylene triethylene composition comprises at least one melt index (I _2), Having a density in the range of 0.950 to 0.960 g / cm ³ , and 1 or more g ′). A product according to the present invention comprises the high-density polyethylene composition of the present invention described above, and such product can be made by compression molding, injection molding, injection blow molding, or injection stretch blow molding.

In one embodiment, the present invention provides a high molecular weight polyethylene α-olefin having a density in the range of 0.915 to 0.940 g / cm ³ and a melt index (I _21.6 ) in the range of 0.5 to 10 g / 10 minutes. High density polyethylene composition comprising a copolymer and a low molecular weight ethylene-based polymer having a density in the range of 0.965 to 0.980 g / cm ³ and a melt index (I ₂ ) in the range of 50 to 1500 g / 10 minutes The high density polyethylene composition of the present invention has a melt index (I ₂ ) of at least 1 g / 10 min, a density in the range of 0.950 to 0.960 g / cm ³ , and a g ′ of 1 or more. .

In another embodiment, the present invention further provides a method for producing a high density polyethylene composition comprising the following steps: (1) ethylene, and one or more α-olefin comonomers in a first reaction. Introducing into the apparatus; (2) (co) polymerizing ethylene in the presence of one or more α-olefin comonomers in the first reactor, whereby 0.915 to 0.940 g / cm ³ Producing a high molecular weight ethylene α-olefin copolymer having a density in the range and a melt index (I ₂₁ ) in the range of 0.5 to 10 g / 10 min; (3) a high molecular weight ethylene α-olefin copolymer; And introducing further ethylene into the second reactor; (4) polymerizing further ethylene in the second reactor, thereby 0.965 to 0.980 g / step to produce the low molecular weight ethylene polymer having a density in the range of m ^3, and 50 to 1500 g / 10 min in the range of melt index (I _2); and (5) thereby stage of producing a high-density polyethylene composition (The high density polyethylene composition has a melt index (I ₂ ) of at least 1, a density in the range of 0.950 to 0.960 g / cm ³ , and one or more g ′).

In another alternative embodiment, the present invention provides a product comprising a high density polyethylene composition, wherein the high density polyethylene composition has a density in the range of 0.915 to 0.940 g / cm ³ , and High molecular weight polyethylene α-olefin copolymer having a melt index (I _21.6 ) in the range of 5-10 g / 10 min, and a density in the range of 0.965-0.980 g / cm ³ , and 50-1500 g / 10 min. A low molecular weight ethylene-based polymer having a melt index (I ₂ ) in the range of from about 1 g / 10 min to a melt index (I ₂ ) of from 0.950 to 0.960 g / cm. ^{It has} a density in the range of ³ and a g 'of 1 or more.

In another alternative embodiment, the present invention provides a method of making a product comprising the following steps: (1) a density in the range of 0.915 to 0.940 g / cm ³ and 0.5 to 10 g / cm. High molecular weight ethylene α-olefin copolymer having a melt index (I _21.6 ) in the range of 10 minutes, a density in the range of 0.965 to 0.980 g / cm ³ and a melt index in the range of 50 to 1500 g / 10 minutes ( Providing a high density polyethylene composition comprising a low molecular weight ethylene-based polymer having I ₂ ), wherein the high density polyethylene composition has a melt index (I ₂ ) of at least 1 g / 10 min, 0.950-0 density in the range of .960g / cm ^3, and having 1 or more g '); (2) compression molding the high-density polyethylene composition, an injection molding, injection blow Form or injection stretch stage blow molding; (3) steps thereby forming a product.

  In one alternative embodiment, the present invention provides a high density polyethylene composition according to any preceding embodiment, except that the second reactor is substantially free of any other α-olefin copolymer. A method of manufacturing the same is provided.

In another embodiment, the present invention is according to any preceding embodiment, except that the high molecular weight polyethylene α-olefin copolymer has a density in the range of 0.920 to 0.940 g / cm ³ . High density polyethylene compositions, methods of making the same, products made therefrom, and methods of making such products are provided.

In another alternative embodiment, the present invention is according to any preceding embodiment, except that the high molecular weight polyethylene α-olefin copolymer has a density in the range of 0.921 to 0.936 g / cm ^3. , High density polyethylene compositions, methods of making the same, products made therefrom, and methods of making such products.

In another alternative embodiment, the present invention relates to any preceding embodiment, except that the high molecular weight polyethylene α-olefin copolymer has a melt index (I _21.6 ) in the range of 1-7 g / 10 min. In accordance with the present invention, a high density polyethylene composition, a method of manufacturing the same, a product made therefrom, and a method of making such a product are provided.

In another alternative embodiment, the present invention relates to any of the preceding, except that the high molecular weight polyethylene α-olefin copolymer has a melt index (I _21.6 ) in the range of 1.3 to 5 g / 10 min. In accordance with embodiments, high density polyethylene compositions, methods of making the same, products made therefrom, and methods of making such products are provided.

In another alternative embodiment, the present invention provides a high density polyethylene according to any preceding embodiment, except that the low molecular weight ethylene-based polymer has a density in the range of 0.970 to 0.975 g / cm ^3. Compositions, methods of making the same, products made therefrom, and methods of making such products are provided.

In another alternative embodiment, the present invention provides a high density according to any preceding embodiment, except that the low molecular weight ethylene-based polymer has a melt index (I ₂ ) in the range of 100-1500 g / 10 min. Polyethylene compositions, methods of making the same, products made therefrom, and methods of making such products are provided.

In another alternative embodiment, the present invention provides a high density according to any preceding embodiment, except that the low molecular weight ethylene-based polymer has a melt index (I ₂ ) in the range of 200-1500 g / 10 min. Polyethylene compositions, methods of making the same, products made therefrom, and methods of making such products are provided.

In another alternative embodiment, the present invention provides that the high-density polyethylene composition has a melt index (I ₂ ) in the range of _1-2 g / 10 minutes; or alternatively, a melt index (I ₂ ) of at least 2 g / 10 minutes. ₂ ), a high density polyethylene composition, a method of making it, a product made therefrom, and a method of making such a product are provided according to any preceding embodiment.

  In another alternative embodiment, the present invention provides a high density, in accordance with any preceding embodiment, except that the high molecular weight ethylene alpha-olefin copolymer has a molecular weight in the range of 150,000 to 375,000. Polyethylene compositions, methods of making the same, products made therefrom, and methods of making such products are provided.

  In another alternative embodiment, the present invention provides a high density polyethylene composition according to any preceding embodiment, except that the low molecular weight ethylene-based polymer has a molecular weight in the range of 12,000 to 40,000. Methods of manufacturing it, products made therefrom, and methods of making such products are provided.

In another alternative embodiment, the present invention provides a high molecular weight polyethylene α-olefin copolymer having a density in the range of 0.921 to 0.936 g / cm ³ and a melt in the range of 1.3 to 5 g / 10 minutes. The low molecular weight ethylene polymer has an index (I _21.6 ), a density in the range of 0.970 to 0.975 g / cm ³ , and a melt index (I ₂ ) in the range of 200 to 1500 g / 10 min. Except, provided is a high density polyethylene composition, a method of making it, a product made therefrom, and a method of making such product, according to any preceding embodiment.

  In another alternative embodiment, the present invention provides for any of the preceding options, except that both the high molecular weight polyethylene alpha-olefin copolymer and the low molecular weight ethylene-based polymer are substantially free of any long chain branching. In accordance with embodiments of the present invention, a high density polyethylene composition, a method of making it, a product made therefrom, and a method of making such a product are provided.

  In another alternative embodiment, the present invention provides a high density polyethylene composition according to any preceding embodiment, except that the high density polyethylene composition is substantially free of any long chain branches, , A product made therefrom, and a method of making such a product.

  In another alternative embodiment, the invention provides that the high-density polyethylene composition has a single ATREF temperature peak, the ATREF temperature peak having a temperature peak maximum between 90 ° C. and 105 ° C .; And the high density polyethylene composition has a calculated high density fraction in the range of 20 percent to 50 percent, said calculated high density fraction being [(2) X (temperature peak maximum in ATREF-DV The weight ratio of the high density polyethylene eluting at the above temperature)]; and the high density polyethylene composition has a minimum relative viscosity average molecular weight log at about 90 ° C. at ATREF-DV; And the high density polyethylene composition has a regression analysis slope of a log of relative viscosity average molecular weight vs. ATREF-DV viscosity vs. temperature less than about 0 and its elution temperature A high density polyethylene composition, a method of making it, a product made from it, and making such a product, according to any preceding embodiment, except that it is measured between 70 ° C and 90 ° C Provide a method.

In another alternative embodiment, the invention provides that the high density polyethylene composition is [(−228.41 ^* density of the high density polyethylene composition) +219.36)] ^* [1 (weight percent) / (g / high density polyethylene composition according to any preceding embodiment, except that it has a comonomer content of weight percent greater than or equal to cm ³ )] and the density is measured in g / cm ³ , a method of making it , Products made therefrom, and methods of making such products.

In another alternative embodiment, the present invention provides that the high density polyethylene composition is [(2750 ^* density of the high density polyethylene composition) -2552.2] ^* [1 (percent) / (g / cm ³ )]. A high density polyethylene composition, a method of making it, and then according to any preceding embodiment, except that it has the following percent ATREF high density fraction, the density being measured in g / cm ^3: Produced products and methods of making such products are provided.

  In another alternative embodiment, the invention provides that the product is at least 150 hours as measured by ASTM D-1693 condition B, 10 percent Igepal, or measured by ASTM D-1693 condition B, 100 percent Igepal. Provided are products and methods of making the products according to any preceding embodiment, except that they have an environmental stress crack resistance of at least 300 hours.

  In another alternative embodiment, the present invention provides a product and a method of making the product according to any preceding embodiment, except that the product is a closure device, a wire cable jacket, a conduit, or a bottle. provide.

  In another alternative embodiment, the present invention provides a product according to any preceding embodiment, except that the product is a compression molded article, an injection molded article, an injection blow molded article, or an injection stretch blow molded article. Provide a method of making a product.

  In another alternative embodiment, the present invention provides a compression molded or injection molded article and a method of making a compression molded or injection molded article according to any preceding embodiment, except that the product is a bottle cap. To do.

  In another alternative embodiment, the invention includes any preceding implementation, except that the product includes a skirt that extends axially from the periphery of the bottom and has a female thread for securing the cap to the container. According to a form, a compression molded or injection molded article and a method of making a compression molded or injection molded article are provided.

  In another embodiment, the present invention precedes, except that the product is a compression molded cap that includes a skirt extending axially from the periphery of the bottom and having an internal thread for securing the cap to the container. Provided are compression molded articles and methods of making compression molded articles according to any embodiment.

  In another alternative embodiment, the present invention includes a skirt that extends axially from the periphery of the bottom, except that the preceding is an injection molded cap with an internal thread for securing the cap to the container. An injection molded article and a method of making an injection molded article are provided according to any embodiment that does.

  In another alternative embodiment, the present invention provides a blow molded article and a method of making a blow molded article according to any preceding embodiment, except that the product is an injection blow molded bottle.

  For the purpose of illustrating the invention, there are shown in the drawings embodiments which are presently preferred; however, it is to be understood that the invention is not limited to the precise arrangements and instrumentalities shown.

DETAILED DESCRIPTION OF THE INVENTION The high density polyethylene composition of the present invention comprises a first component and a second component. The first component is a high molecular weight ethylene α-olefin copolymer having a density in the range of 0.915 to 0.940 g / cm ³ and a melt index (I ₂₁ ) of 0.5 to 10 g / 10 min. Is preferred. The second component is preferably a low molecular weight ethylene polymer having a density in the range of 0.965 to 0.980 g / cm ³ and a melt index (I ₂ ) in the range of 50 to 1500 g / 10 minutes. The high density polyethylene composition has a melt index (I ₂ ) of at least 1 g / 10 min, a density in the range of 0.950 to 0.960 g / cm ³ , and a g ′ of 1 or more. The high density polyethylene composition further comprises additional components, additives, or adjuvants. The high density polyethylene composition is a bimodal polymer, or alternatively, the high density polyethylene is a multimodal polymer.

  The term “bimodal” as used herein indicates that the molecular weight distribution (MWD) of a gel permeation chromatography (GPC) curve exhibits a two component polymer, eg two peaks, or one component polymer is the other component polymer. It can be present as a hump, shoulder, or tail for the MWD of the other; or alternatively, for example, it can mean that the two components can have only one peak that does not have a hump, shoulder, or tail.

  The term “multimodal” as used herein refers to a component polymer having a GPC curve MWD greater than 2, eg, 3 or more peaks, or one component polymer relative to the MWD of the other component polymer. It may be present as a hump, shoulder, or tail; alternatively, it means that three or more components may have a single peak that does not have a hump, shoulder, or tail.

The term “polymer” is used herein to indicate a homopolymer, interpolymer (or copolymer), or terpolymer. The term “polymer” as used herein includes interpolymers such as those made by copolymerization of ethylene with one or more C ₃ -C ₂₀ α-olefin (s).

  The term “interpolymer” as used herein refers to polymers prepared by polymerization of at least two different types of monomers. Thus, the generic term interpolymer generally includes polymers prepared from two different types of monomers, and copolymers used to refer to polymers prepared from more than two different types of monomers.

  The term (co) polymerization refers herein to the polymerization of ethylene in the presence of one or more α-olefin copolymers.

The first component is a polymer; for example, a polyolefin. The first component is preferably an ethylene polymer; for example, the first component is preferably a high molecular weight ethylene α-olefin copolymer. The first component is substantially free of any long chain branches. As used herein, substantially free of any long chain branches is preferably less than about 0.1 long chain branches per 1000 total carbons, more preferably about 1000 per 1000 total carbons. Refers to an ethylene-based polymer that is substituted with less than 0.01 long chain branches. The presence of long chain branching is generally determined by methods known in the art, such as gel permeation chromatography in combination with a low angle light scattering detector (GPC-LALLS) and gel permeation chromatography in combination with a differential viscometer detector ( GPC-DV). The first component has a density in the range of 0.915 to 0.940 g / cm ³ . All individual values and subranges from 0.915 to 0.940 g / cm ³ are included herein and disclosed herein. For example, the first component has a density in the range of 0.920 to 0.940 g / cm ³ , or alternatively, the first component has a density in the range of 0.921 to 0.936 g / cm ^3. . The first component has a melt index (I _21.6 ) in the range of 0.5 to 10 g / 10 minutes. All individual values and subranges from 0.5 to 10 g / 10 min are included herein and disclosed herein. For example, the first component has a melt index (I _21.6 ) in the range of 1-7 g / 10 minutes, or alternatively, the first component has a melt index (I _{21.6 in} the range of 1.3-5 g / 10 minutes). ). The first component has a molecular weight in the range of 150,000 to 375,000. All individual values and subranges from 150,000 to 375,000 are included herein and disclosed herein. For example, the first component has a molecular weight in the range of 175,000 to 375,000; alternatively, the first component has a molecular weight in the range of 200,000 to 375,000. The first component may comprise any amount of one or more α-olefin copolymers. For example, the first component includes less than about 10% by weight of one or more α-olefin copolymers, based on the weight of the first component. All individual values and subranges less than 10 weight percent are included herein and disclosed herein. The first component may comprise any amount of ethylene. For example, the first component includes at least about 90 wt% ethylene, based on the weight of the first component. All individual values and subranges greater than 90 weight percent are included herein and disclosed herein. For example, the first component includes at least 95% by weight ethylene, based on the weight of the first component.

  Alpha-olefin copolymers generally contain only 20 carbon atoms. For example, the α-olefin copolymer preferably has 3 to 10 carbon atoms, and more preferably 3 to 8 carbon atoms. Exemplary α-olefin copolymers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, And 4-methyl-1-pentene. The α-olefin copolymer is preferably selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene, and more preferably selected from the group consisting of 1-hexene and 1-octene. preferable.

The second component is a polymer; for example, a polyolefin. The second component is preferably an ethylene-based polymer; for example, the second component is preferably a low molecular weight ethylene homopolymer. The ethylene homopolymer may contain a small amount of a mixed copolymer such as an α-olefin copolymer. As used herein, the term ethylene homopolymer refers to an ethylene-based polymer containing at least 99% by weight of ethylene units. It is preferred that the second component is substantially free of any long chain branching. As used herein, substantially free of any long chain branches means that the ethylene-based polymer preferably has less than about 0.1 long chain branches per 1000 total carbons, more preferably all carbons. It refers to being substituted with less than about 0.01 long chain branches per 1000. The presence of long chain branches is generally determined according to methods known in the art as described above. The second component has a density in the range of 0.965 to 0.980 g / cm ³ . All individual values and subranges from 0.965 to 0.980 g / cm ³ are included herein and disclosed herein. For example, the second component has a density in the range of 0.970 to 0.975 g / cm ³ . The second component has a melt index (I ₂ ) in the range of 50-1500 g / 10 minutes. All individual values and subranges from 50 to 1500 g / 10 min are included herein and disclosed herein. For example, the second component has a melt index (I ₂ ) in the range of 200-1500 g / 10 minutes, or alternatively, the second component has a melt index (I ₂ ) in the range of 500-1500 g / 10 minutes. Have. The second component has a molecular weight in the range of 12,000 to 40,000. Individual values and subranges from 12,000 to 40,000 are included herein and disclosed herein. For example, the second component has a molecular weight in the range of 15,000 to 40,000, or alternatively, the second component has a molecular weight in the range of 20,000 to 40,000. The second component comprises less than 1.00% by weight of one or more α-olefin copolymers, based on the weight of the second component. All individual values and subranges less than 1.00 weight percent are included herein and disclosed herein. For example, the second component may comprise 0.0001 to 1.00% by weight of one or more alpha-olefin copolymers; the second component is 0.001 to 1.00% by weight of 1 Or more α-olefin copolymers may be included. The second component includes at least about 99% ethylene by weight, based on the weight of the second component. All individual values and subranges from 99 to 100 weight percent are included herein and disclosed herein. For example, the second component includes 99.5 to 100 weight percent ethylene, based on the weight of the second component.

The high density polyethylene composition has a density in the range of 0.950 to 0.960 g / cm ³ . All individual values and subranges from 0.950 to 0.960 g / cm ³ are included herein and disclosed herein. The high density polyethylene composition has a melt index (I ₂ ) of at least 1 g / 10 minutes. All individual values and subranges above 1 g / 10 min are included herein and disclosed herein. For example, the high density polyethylene composition has a melt index (I ₂ ) in the range of _1-2 g / 10 minutes, or alternatively, the high density polyethylene composition has a melt index (I ₂ ) of at least 2 g / 10 minutes. . The high density polyethylene composition is substantially free of any long chain branches. As used herein, substantially free of any long chain branches is preferably less than about 0.1 long chain branches per 1000 total carbons, more preferably about 1000 per 1000 total carbons. Refers to a polyethylene composition that is substituted with less than 0.01 long chain branches. The presence of long chain branches is generally determined according to methods known in the art as described above. The high density polyethylene composition has a molecular weight distribution in the range of 6-25. All individual values and subranges from 6 to 25 are included herein and disclosed herein. For example, the high density polyethylene composition has a molecular weight distribution in the range of 7-20, or alternatively, the high density polyethylene composition has a molecular weight distribution in the range of 7-17. The term molecular weight distribution, or “MWD”, refers herein to the ratio of the weight average molecular weight (M _w ) to the number average molecular weight (M _n ), ie (M _w / M _n ), and is described in more detail below. Explained. The high density polyethylene composition has an environmental stress crack resistance of at least 150 hours as measured by ASTM D-1693 condition B, 10 percent Igepal, or preferably by ASTM D-1693 condition B, 10 percent Igepal. It has an environmental stress crack resistance of at least 200 hours as measured, or more preferably has an environmental stress crack resistance of at least 250 hours as measured by ASTM D-1693 Condition B, 10 percent Igepal. In an alternative, the high density polyethylene composition has an environmental stress crack resistance of at least 300 hours as measured by ASTM D-1693 condition B, 100 percent Igepal, or preferably at least 400 hours ASTM D-1693 condition. B, has an environmental stress crack resistance of at least 400 hours as measured by 100 percent Igepal, or more preferably at least 500 hours of environmental stress crack as measured by ASTM D-1693, Condition B, 100 percent Igepal Has resistance. The high density polyethylene composition may include any amount of the first component, the second component, or a combination thereof. The high density polyethylene composition comprises 40-60 wt% of the first component, based on the total weight of the first component and the second component. All individual values and subranges from 40 to 60 weight percent are included herein and disclosed herein. For example, the high density polyethylene composition comprises 42-55% by weight of the first component, based on the total weight of the first and second components. The high density polyethylene composition further comprises 40-60% by weight of the second component, based on the total weight of the first component and the second component. All individual values and subranges from 40 to 60 weight percent are included herein and disclosed herein. For example, the high density polyethylene composition further comprises 48-55% by weight of the second component, based on the total weight of the first component and the second component. Preferably, the high density polyethylene composition has a single ATREF temperature peak, and the ATREF temperature peak has a temperature peak maximum between 90 ° C. and 105 ° C., as described in more detail below. The high density polyethylene composition further has a calculated high density fraction ranging from 20 percent to 50 percent. All individual values and subranges from 20 percent to 50 percent are included herein and disclosed herein. The calculated high-density fraction is referred to herein as [(2) X (weight ratio of high-density polyethylene eluting at a temperature equal to or higher than the temperature peak maximum value in ATREF-DV)]. Further, the high density polyethylene composition has a minimum of the log of relative viscosity average molecular weight at about 90 ° C. at ATREF-DV, and regression analysis of the log of relative viscosity average molecular weight vs. ATREF-DV viscosity vs. temperature of less than about 0. It has a slope and its elution temperature is measured between 70 ° C and 90 ° C.

  The ATREF high density fraction (percent) of the polyethylene composition is calculated by integrating the area under the curve at 86 ° C. and above unless there is a local minimum in the curve. Neither the inventive sample or the comparative sample measured and reported in the table had a local minimum on the temperature curve at 86 ° C. and above.

  The high density polyethylene composition has one or more g 'averages as measured by gel permeation chromatography (GPC) with triple detector, described in further detail below. g 'is expressed as the ratio of the intrinsic viscosity of the high density polyethylene composition of the present invention to the intrinsic viscosity of the linear polymer control. If g 'is 1 or greater, the sample being analyzed is considered linear, and if g' is less than 1, it is a branched polymer as compared to a linear polymer by definition. However, current test methods are prone to errors in their accuracy and precision; therefore, appropriate measures need to take into account such precision errors. Therefore, a small deviation from 1, for example a value of 0.012 or less, ie 0.988 to 1.012, is still defined as a linear polymer. In the alternative, a small deviation from 1, for example a value of 0.025 or less, ie 0.975 to 1.025, is still defined as a linear polymer.

Referring to FIG. 1, a high density polyethylene composition has an ATREF high of less than [(2750 ^* density of high density polyethylene composition) -2552.2] ^* [1 (percent) / (g / cm ³ )]. Has a density fraction (density is measured in g / cm ³ ).

Referring to FIG. 2, the high-density polyethylene composition has a [(−228.41 ^* density of the high-density polyethylene composition) +219.36)] ^* [1 (weight percent) / (g / cm ³ )] or more. It has a weight percent comonomer content (density is measured in g / cm ³ ).

Referring to FIG. 3, the calculated high density fraction expressed as a percentage is equal to [1107.4 ^* (density of high molecular weight polyethylene component) −992.56] ^* [1 (percent / cm ³ ).

Referring to FIG. 4, FIG. 4 illustrates the relationship between the elution temperature expressed in ° C. and the viscosity average expressed in Log [M _v (g / mol)].

  The high density polyethylene composition may further include additional components such as other polymers, adjuvants, and / or additives. Such adjuvants or additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, extenders, dyes, primary antioxidants, secondary antioxidants, processing aids. Agents, UV stabilizers, nucleating agents, and combinations thereof. The high density polyethylene composition includes less than about 10 weight percent of one or more additives combined, based on the weight of the high density polyethylene composition. All individual values and subranges less than about 10 weight percent are included herein and disclosed herein. For example, the high density polyethylene composition includes less than about 5 weight percent of one or more additives combined, based on the weight of the high density polyethylene composition, or alternatively, the high density polyethylene composition includes the high density polyethylene composition. Based on the weight of the product, comprising less than about 1 weight percent of one or more additives combined, or in another alternative, the high density polyethylene composition is based on the weight of the high density polyethylene composition. One or more additives combined may comprise less than about 0.5 weight percent. Antioxidants such as Irgafos® 168 and Irganox® 1010 are often used to protect polymers from thermal and / or oxidative degradation reactions. Irganox® 1010 is tetrakis (methylene (3,5-di-tert-butyl-4hydroxyhydrocinnamate) and is commercially available from Ciba Geigy Inc. Irgafos® 168 is tris ( 2,4 di-tert-butylphenyl) phosphite, commercially available from Ciba Geigy Inc.

  The high density polyethylene composition of the present invention can be further blended with other polymers. Such other polymers are generally known to those skilled in the art. Blends comprising the high density polyethylene compositions of the present invention are formed by any conventional method. For example, the selected polymer is melt blended with a single or twin screw extruder, or a mixer such as a Banbury mixer, a Haake mixer, a Barbender internal mixer.

  In general, blends containing the inventive high density polyethylene composition comprise at least 40% by weight of the inventive high density polyethylene composition, based on the total weight of the blend. Individual values and subranges within the range of at least 40 weight percent are included herein and disclosed herein. For example, the blend comprises at least 50% by weight of the inventive high density polyethylene composition, based on the total weight of the blend; alternatively, the blend is at least 60% by weight of the invention, based on the total weight of the blend. Or alternatively, based on the total weight of the blend, the blend comprises at least 70% by weight of the high density polyethylene composition of the present invention; alternatively, the blend is based on the total weight of the blend. On the basis of at least 80% by weight of the inventive high density polyethylene composition; alternatively, based on the total weight of the blend, the blend comprises at least 90% by weight of the inventive high density polyethylene composition; Alternatively, the blend is at least 95 wt. Comprising ethylene composition; or alternatively, a blend, based on the total weight of the blend, including high-density polyethylene composition at least 99.99% by weight of the present invention.

  A variety of polymerization reactions and catalyst systems can be used to produce the high density polyethylene composition of the present invention. Typical transition metal catalyst systems used to prepare high density polyethylene compositions are magnesium / titanium based catalyst systems typically shown in the catalyst systems described in US Pat. No. 4,302,565; Vanadium-based catalyst systems are described, for example, in US Pat. No. 4,508,842; US Pat. No. 5,332,793; US Pat. No. 5,342,907; and US Pat. No. 5,410,003. And metallocene catalyst systems such as those described in US Pat. No. 4,937,299; US Pat. No. 5,317,036; and US Pat. No. 5,527,752. A catalyst system using molybdenum oxide on a silica-alumina support is also useful. Preferred catalyst systems for preparing the components for the high density polyethylene compositions of the present invention are Ziegler-Natta catalyst systems and metallocene catalyst systems.

  In some embodiments, the preferred catalyst used in the process for making the high density polyethylene composition is a magnesium / titanium type catalyst. In particular, for gas phase polymerization, the catalyst is made from a precursor comprising magnesium chloride and titanium chloride in an electron donor solvent. This solution is often deposited on a porous catalyst support or a filler is added, which provides additional mechanical strength to the particles in subsequent spray drying. Solid particles from either support method are often slurried in a diluent to produce a high viscosity mixture and then used as the catalyst precursor. Exemplary catalyst types are described in US Pat. No. 6,187,866 and US Pat. No. 5,290,745, the entire contents of both being included herein. Precipitated / crystallized catalyst systems, such as those described in US Pat. No. 6,511,935 and US Pat. No. 6,248,831, may be used, the entire contents of both of which are described herein. Included in. Such a catalyst may be further modified with one precursor activator. Such further modifications are described in US Patent Application Publication No. 2006/0287445 A1.

Preferably, the catalyst precursor is of the formula Mg _d Ti (OR) _e X _f (ED) _{g where} R is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms or COR ′. R ′ is an aliphatic or aromatic hydrocarbon group having 1 to 14 carbon atoms; each OR group is the same or different; X is independently chlorine, bromine or iodine; ED is An electron donor; d is 0.5 to 56; e is 0, 1 or 2; f is 2 to 116; and g is greater than 2 up to 1.5 ^* d + 3). It is prepared from a titanium compound, a magnesium compound, and an electron donor.

  The electron donor is an organic Lewis base that is liquid at temperatures ranging from 0 ° C. to 200 ° C., and magnesium and titanium compounds are soluble therein. Electron donor compounds are sometimes referred to as Lewis bases. The electron donor may be an alkyl ester of an aliphatic or aromatic carboxylic acid, an aliphatic ketone, an aliphatic amine, an aliphatic alcohol, an alkyl or cycloalkyl ether, or a mixture thereof, each electron donor having 2 to 2 It has 20 carbon atoms. Preferred among these electron donors are alkyl and cycloalkyl ethers having 2 to 20 carbon atoms; dialkyl, diaryl, and alkylaryl ketones having 3 to 20 carbon atoms; Alkyl, alkoxy, and alkyl alkoxy esters of alkyl and aryl carboxylic acids having 20 carbon atoms. The most preferred electron donor is tetrahydrofuran. Other examples of suitable electron donors are methyl formate, ethyl acetate, butyl acetate, ethyl ether, dioxane, di-n-propyl ether, dibutyl ether, ethanol, 1-butanol, ethyl formate, methyl acetate, ethyl Anisate, ethylene carbonate, tetrahydropyran, and ethyl propionate.

  While initially using a large excess of the electron donor to obtain the reaction product of the titanium compound and the electron donor, the final catalyst precursor will yield from about 1 to about 20 moles of electron donor per mole of titanium compound. Preferably about 1 to about 10 moles of electron donor per mole of titanium compound.

  Since the catalyst acts as a template for polymer growth, it is essential that the catalyst precursor be converted to a solid. In order to produce polymer particles with a relatively narrow size distribution, a small amount of fines and good flow properties, it is also essential that the resulting solids have an appropriate particle size and shape. This solution comprising a Lewis base, magnesium and titanium compound may be impregnated into a porous carrier and dried to form a solid catalyst, but it is preferred to convert the solution to a solid catalyst by spray drying. Each of these methods thus forms a “supported catalyst precursor”.

The spray dried catalyst product is then optionally placed in a mineral oil slurry. Since the viscosity of the hydrocarbon slurry diluent is sufficiently low, the slurry is conveniently sent through the pre-activator and finally enters the polymerization reactor. The catalyst is supplied using a rasley catalyst feeder. Progressive cavity pumps, such as Moyno pumps, are commonly used in commercial reaction systems, but dual piston syringe pumps are pilot scales with a catalyst flow of 10 cm ³ / hr (2.78 × 10 ⁻⁹ m ³ / s) or less. Generally used in the reaction system of

  A cocatalyst, or activator, is also fed to the reactor to effect polymerization. Full activation with additional cocatalysts is required to achieve full activity. Full activation usually occurs in the polymerization reactor, but techniques taught in EP 1,200,483 may be used.

  Conventionally used cocatalysts as reducing agents are composed of aluminum compounds, but lithium, sodium and potassium compounds, alkaline earth metals, and other earth metal compounds other than aluminum are possible. The compound is usually a hydride compound, an organometallic compound, or a halide compound. Butyl lithium and dibutyl magnesium are examples of useful compounds other than aluminum.

The activator compound is generally used with any of the titanium-based catalyst precursors and has the formula AlR _a X _b H _c , wherein each X is independently chlorine, bromine, iodine, or OR ′; And R ′ are independently saturated aliphatic hydrocarbon radicals having 1 to 14 carbon atoms; b is 0 to 1.5; c is 0 or 1; and a + b + c = 3 ). Preferred activators include alkylaluminum mono- and dichlorides, each alkyl radical having 1 to 6 carbon atoms and a trialkylaluminum. Examples are diethylaluminum chloride and tri-n-hexylaluminum. About 0.10 to 10 moles, and preferably 0.15 to 2.5 moles of activator are used per mole of electron donor. The molar ratio of activator to titanium is in the range of 1: 1 to 10: 1, preferably in the range of 2: 1 to 5: 1.

The hydrocarbyl aluminum cocatalyst is of the formula R ₃ Al or R ₂ AlX, wherein each R is independently alkyl, cycloalkyl, aryl, or hydrogen; at least one R is hydrocarbyl; and 2 or Three R radicals may be linked to form a heterocyclic structure). Each R that is a hydrocarbyl radical may have 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. X is a halogen, preferably chlorine, bromine or iodine. Examples of hydrocarbyl aluminum compounds are as follows: Triisobutylaluminum, tri-n-hexylaluminum, di-isobutyl-aluminum hydride, dihexylaluminum hydride, di-isobutyl-hexylaluminum, isobutyl-dihexylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri- n-butylaluminum, trioctylaluminum, tridecylaluminum, tridodecylaluminum, tribenzylaluminum, triphenylaluminum, trinaphthylaluminum, tritolylaluminum, dibutylaluminum chloride, diethylaluminum chloride, and ethylaluminum sesquichloride. Cocatalyst compounds also serve as activators and modifiers.

  An activator may be added to the precursor before and / or during the polymerization. In one procedure, the precursor is fully activated prior to polymerization. In another procedure, the precursor is partially activated prior to polymerization and activation is complete in the reactor. When a modifier is used in place of an activator, the modifier is usually dissolved in an organic solvent such as isopentane, and when a support is used, the support is impregnated after impregnation of the titanium compound or complex, followed by the supported catalyst precursor. dry. Otherwise, the modifier solution alone is added directly to the reactor. Modifiers are similar in chemical structure and act on the activator as a cocatalyst. For variations, see, for example, US Pat. No. 5,106,926, which is incorporated herein by reference in its entirety. The cocatalyst is preferably added separately to the polymerization reactor as neat or as a solution in an inert solvent, such as isopentane, at the same time as the ethylene flow begins.

In embodiments using supports, the precursors are inorganic oxide supports (eg silica; aluminum phosphate; alumina; silica / alumina mixtures; silica modified with organoaluminum compounds such as triethylaluminum; and silica modified with diethylzinc. ). In some embodiments, silica is a preferred support. Typical carriers are solid, particulate, porous materials that are essentially inert to polymerization. It has an average particle size of 10 to 250 μm, preferably 30 to 100 μm; a surface area of at least 200 m ² / g, preferably at least 250 m ² / g; and a pore size of at least 100 × 10 ⁻¹⁰ m, preferably at least 200 × Used as 10 ^-10 m dry powder. In general, the amount of support used is that which provides 0.1 to 1.0 millimole of titanium per gram of support, preferably 0.4 to 0.9 millimole of titanium per gram of support. Impregnation of the catalyst precursor onto the silica support can be achieved by mixing the precursor and silica gel in an electron donor solvent or other solvent, and then removing the solvent under reduced pressure. If a support is not desired, the catalyst precursor can be used in liquid form.

  In another embodiment, metallocene catalysts, single site catalysts and constrained geometry catalysts can be used in the practice of the present invention. In general, metallocene catalyst compounds include half and full sandwich compounds having one or more π-bonded ligands, including cyclopentadienyl type structures or other similar functional structures such as pentadiene, cyclooctatetra Endiyl and imides are included. Typical compounds are generally one or more ligands capable of pi-bonding with a transition metal atom, usually from groups 3-8, preferably 4, 5 or 6 of the periodic table of elements, or lanthanides and actinides It is described as containing a ligand or moiety derived from cyclopentadienyl in combination with a transition metal selected from the series.

  Exemplary metallocene-type catalyst compounds include, for example, U.S. Patent Nos. 4,530,914; 4,871,705; 4,937,299; 5,017,714; 5,055,438; 5,096,867; 5,120,867; 5,124,418; 5,198,401; 5,210,352 No. 5,229,478; No. 5,264,405; No. 5,278,264; No. 5,278,119; No. 5,304,614; No. 5 No. 5,347,025; No. 5,350,723; No. 5,384,299; No. 5,391,790; No. 5,391,789 No. 5,399,636; No. 5,408,017; No. 5,491,20 No. 5,455,366; No. 5,534,473; No. 5,539,124; No. 5,554,775; No. 5,621,126; No. 5 684,098; 5,693,730; 5,698,634; 5,710,297; 5,712,354; 5,714,427 No. 5,714,555; No. 5,728,641; No. 5,728,839; No. 5,753,577; No. 5,767,209; 770,753 and 5,770,664; European Patent Application Publications EP-A-0591756; EP-A-0520732; EP-A-0420436; EP-A-0485822; EP-A EP-0485823; EP-A-0743324; PC-A-0518092; and PCT publications: WO 91/04257; WO 92/00333; WO 93/08221; WO 93/08199; WO 94/01471; WO 96/20233; WO 97 WO 97/19959; WO 97/46567; WO 98/01455; WO 98/06759 and WO 98/011144. All of these references are incorporated herein by reference in their entirety.

  Suitable catalysts for use herein include constrained geometry catalysts as disclosed in US Pat. Nos. 5,272,236 and 5,278,272, both of which are incorporated by reference in their entirety. It is preferable.

  Monocyclopentadienyl transition metal olefin polymerization catalysts taught in US Pat. No. 5,026,798, the teachings of which are incorporated herein by reference, are also suitable as the catalyst of the present invention.

  The foregoing catalyst can be further described as comprising a metal coordination complex comprising a group 3-10 metal or lanthanide series of the Periodic Table of Elements and a delocalized π bond moiety substituted with a constraint inducing moiety. Such complexes have a geometry constrained around the metal atom. The catalyst further includes an activated cocatalyst.

  Any conventional ethylene homopolymerization or (co) polymerization reaction may be used to produce the high density polyethylene composition of the present invention. Such conventional ethylene homopolymerization or (co) polymerization reactions include, but are not limited to, conventional reactors such as gas phase reactors, loop reactors, stirred tank reactors, and a series of Or gas phase polymerization, slurry phase polymerization, liquid phase polymerization, and combinations thereof using a series and parallel batch reactors. The polymerization system of the present invention is a dual sequential polymerization system or a multi-sequential polymerization system. Examples of dual sequential polymerization systems include, but are not limited to, gas phase polymerization / gas phase polymerization; gas phase polymerization / liquid phase polymerization; liquid phase polymerization / gas phase polymerization; liquid phase polymerization / liquid phase polymerization; Liquid phase polymerization / slurry phase polymerization; slurry phase polymerization / liquid phase polymerization; slurry phase polymerization / gas phase polymerization; and gas phase polymerization / slurry phase polymerization. A multi-sequential polymerization system includes at least three polymerization reactions. The above catalyst system may also be a conventional catalyst system. The high density polyethylene composition of the present invention is preferably made by a dual gas phase polymerization process, such as gas phase polymerization / gas phase polymerization; however, the present invention is not so limited and using any combination of the above Also good.

  For production, a dual sequential polymerization system connected in series as described above may be used. The first component, the high molecular weight ethylene polymer, may be produced in the first stage of the dual sequential polymerization system, and the second component, the low molecular weight ethylene polymer, is prepared in the second stage of the dual sequential polymerization system. May be. Alternatively, the second component, the low molecular weight ethylene-based polymer, may be made in the first stage of the dual sequential polymerization system, and the first component, the high molecular weight ethylene-based polymer, is the second stage of the dual sequential polymerization system. May be made.

  For the purposes of this disclosure, a reactor whose conditions result in the production of a first component is known as a first reactor. Alternatively, a reactor whose conditions result in the production of a second component is known as a second reactor.

For production, a catalyst system comprising a cocatalyst, ethylene, one or more α-olefin copolymers, hydrogen, and optionally an inert gas and / or liquid, such as N ₂ , isopentane, and hexane, The first component / active catalyst mixture is then fed, for example, in batches from the first reactor to the second reactor. Continuously transferred to the reactor. Ethylene, hydrogen, cocatalyst, and optionally inert gases and / or liquids, such as N ₂ , isopentane, hexane, are continuously fed to the second reactor to produce the final product, the high density polyethylene composition of the present invention. Things are withdrawn from the second reactor continuously, for example in batches. A preferred form takes a batch quantity of the first component from the first reactor and transfers them to the second reactor using the differential pressure generated by the regeneration gas compression system. The high density polyethylene composition of the present invention is then transferred to a purge bin under inert atmosphere conditions. Thereafter, residual hydrocarbons are removed and moisture is introduced to reduce any residual aluminum alkyl and any residual catalyst before the high density polyethylene composition of the present invention is exposed to oxygen. Next, the high-density polyethylene composition of the present invention is transferred to an extruder and pelletized. Such pelletizing techniques are generally known. The high density polyethylene composition of the present invention can be further melt screened. After the melting process in the extruder, the molten composition is passed through one or more active screens (positioned more than one in succession) (each active screen is 5-100 pounds / hr / in ^2). (1.0 to about 20 kg / s / m ² ) with a mass flux of 2 to 400 (2 to 4 × 10 ⁻⁵ m), preferably 2 to 300 (2 to 3 × 10 ⁻⁵ m), most Preferably, it has a micron retention size of 2 to 70 (2 to 7 × 10 ⁻⁶ m)). Such additional melt screening is disclosed in US Pat. No. 6,485,662, which is incorporated herein by reference to the extent that it discloses melt screening.

In another production, a multi-sequential polymerization system connected in series and in parallel as described above may be used. In one embodiment of the present invention, a co-catalyst, ethylene, a catalyst system comprising one or more of the α- olefin copolymer, hydrogen, and optionally inert gases and / or liquids, for example N _2, isopentane, and hexane Is continuously fed to the first reactor connected to the second reactor (the second reactor is continuously connected to the third reactor); first component / activity The catalyst mixture is then continuously transferred, for example in a batch, from the first reactor to the second reactor and then to the third reactor. Ethylene, hydrogen, cocatalyst, and optionally inert gases and / or liquids, such as N ₂ , isopentane, and hexane, are continuously fed to the second and third reactors, and further the end product, ie The high density polyethylene composition is removed from the third reactor continuously, for example in batches. A preferred form is to take a batch quantity of the first component from the first reactor, transfer them to the second reactor, then take a batch from the second reactor and transfer them to the recycle gas compression system ( Transfer to the third reactor using the differential pressure generated by the recycled gas compression system). Alternatively, the first reactor is fed in parallel with the second and third reactors, and the product from the first reactor is transferred to either the second or third reactor. The high density polyethylene composition is then transferred to a purge bottle under inert atmosphere conditions. Thereafter, residual hydrocarbons are removed and moisture may be introduced to reduce any residual aluminum alkyl and any residual catalyst before the polymer, the high density polyethylene composition of the present invention, is exposed to oxygen. Next, the high-density polyethylene composition of the present invention is moved to an extruder and pelletized. Such pelletizing techniques are generally known. The high density polyethylene composition of the present invention can be further melt screened. After the melting process in the extruder, the molten composition is passed through one or more active screens (positioned more than one in succession) (each active screen is 5-100 pounds / hr / in ^2). (1.0 to about 20 kg / s / m ² ) with a mass flux of 2 to 400 (2 to 4 × 10 ⁻⁵ m), preferably 2 to 300 (2 to 3 × 10 ⁻⁵ m), most Preferably, it has a micron retention size of 2 to 70 (2 to 7 × 10 ⁻⁶ m)). Such additional melt screening is disclosed in US Pat. No. 6,485,662, which is incorporated herein by reference to the extent that it discloses melt screening.

  In another alternative manufacturing method, the high density polyethylene composition of the present invention is a polymer made in two or more independent reactors (each using the same or different catalyst) by post reaction blending. Can be manufactured from.

  For application, the high-density polyethylene composition of the present invention can be used to produce shaped articles. Such products include, but are not limited to, closure devices such as bottle caps, wire cable jackets, conduits, or injection blow molded articles. Various methods can be used to produce products such as bottle caps, wire cable jackets, conduits, or injection blow molded articles such as injection blow molded bottles. Suitable conversion techniques include, but are not limited to, wire coating, pipe extrusion, blow molding, coextrusion blow molding, injection molding, injection blow molding, injection stretch blow molding, compression molding, extrusion, pultrusion, and Calendaring. Such techniques are generally well known. Preferred conversion techniques include wire coating, pipe extrusion, injection blow molding, compression molding, and injection molding.

  In the compression molding process, a two-piece mold provides a cavity in the shape of the desired molded part. Heat the mold. An appropriate amount of the inventive high density polyethylene composition, preferably in molten form, is filled into the lower half of the mold. Two mold parts are brought together under pressure. The inventive high density polyethylene composition softened by heat is thereby welded to a continuous mass in the shape of a cavity. The continuous mass is hardened by cooling in the mold under pressure, thereby forming a compression molded product, for example a bottle cap. The compression molded cap may include a skirt extending axially from the periphery of the bottom and may further include an internal thread for securing the cap to the container.

  In the injection molding process, the high density polyethylene composition of the present invention is fed to the extruder via a hopper. The extruder conveys, heats, melts and presses the high density polyethylene composition of the present invention to form a melt stream. The melt stream is extruded from the extruder through a nozzle into a relatively cool mold that is kept closed under pressure, thereby filling the mold. The melt cools and hardens and hardens completely. Next, the mold is opened and a molded product, for example, a bottle cap is taken out. The injection molded cap may include a skirt that extends axially from the periphery of the bottom and may further include an internal thread for securing the cap to the container.

  In a blow molding process, such as injection blow molding, the high density polyethylene composition of the present invention is melted and then formed into a tube or parison by injection molding. The end of the tube or parison is sealed except to the extent that blown air can enter. A sealed tube or parison is inflated inside the mold, thereby taking the form of the mold. Molded articles, such as bottles, are cooled and then discharged from the mold. If necessary, the molded article is then deburred.

  Closure devices, such as bottle caps, comprising the high density polyethylene composition of the present invention exhibit improved environmental crack resistance. Such bottle caps are adapted to withstand the pressure of carbonated beverages. Such bottle caps also have bottle closures and seals (i.e. the optimum torque provided by the machine to screw the bottle caps) or the bottle seals (i.e. Smoothen the optimum torque).

  Of course, the present invention may be practiced in the absence of any ingredients not specifically disclosed. The following examples are provided to further illustrate the present invention and are not to be construed as limiting.

Examples 1 to 6 of the present invention
Examples 1-6 of the present invention were prepared according to the following procedure. A dual sequential polymerization system, for example, a second gas phase reactor operating continuously with the first gas phase reactor was prepared. Ethylene, one or more α- olefin copolymer, hydrogen, catalyst was slurried in mineral oil, for example, Ziegler-Natta catalysts, N _2, and isopentane were fed continuously into the first reactor. Thereafter, a cocatalyst, such as triethylaluminum (TEAL), was continuously fed to the first reactor to activate the catalyst. A first polymerization reaction of ethylene was conducted in the presence of 1-hexene in the first reactor under the conditions shown in Table I below, thereby producing a first component-catalyst complex. The first component-catalyst complex was continuously transferred to the second reactor. Additional ethylene, hydrogen, cocatalyst such as TEAL, N ₂ , and isopentane were fed continuously to the second reactor. No additional catalyst was added to the second reactor. A second polymerization reaction of ethylene was conducted in a second reactor under the conditions shown in Table I below, thereby producing a first component-catalyst-second component complex. The first component-catalyst-second component complex is continuously removed from the second reactor in batches and placed in a product chamber where it is purged to remove residual hydrocarbons and then fiberpak. ) Moved to drum. The fiber pack drum was continuously purged with humidified nitrogen. This polymer, the high density polyethylene composition of the present invention, was further processed with a mixer / pelletizer. Additional additives shown in Table III were added to the polymer, the high density polyethylene composition of the present invention. The polymer, the high density polyethylene composition of the present invention, was melted in a mixer and the additive was dispersed in the polymer, the high density polyethylene composition matrix of the present invention. The high density polyethylene composition of the present invention was extruded through a die plate, pelletized and cooled. Resin samples of Examples 1-6 of the present invention were tested for their properties from pellets or formed into test plaques according to ASTM D-4703-00 and then tested for their properties. Such properties are shown in Tables I and II and FIGS.

Comparative Examples A to E
Comparative Example A is commercially available from Borealis AIS, Denmark under the trade name Borstar® MB6561. Comparative Example B is commercially available from BP Solvay Polyethylene under the trade name Rigidex® HD 5130 EA-B. Comparative Example C is commercially available from The Dow Chemical Company, USA under the trade name XZ 89719.01. Comparative Example D is commercially available from Basell, Germany under the trademark Hostaen® GX4027. Comparative Example E is commercially available from The Dow Chemical Company, USA under the trade name XZ 89719.00. The resin samples of Comparative Examples A-E were tested for their properties from the pellets or formed into test plaques according to ASTM D-4703-00 and then tested for their properties. Resin samples of Comparative Examples A-E and plaques made therefrom were tested for their properties. Such properties are shown in Table IV.

Test Methods Unless otherwise noted, the values reported herein were measured according to the following test methods.

The density (g / cm ³ ) was measured in isopropanol according to ASTM-D 792-03, Method B. Specimens were measured within 1 hour of molding after conditioning in an isopropanol bath at 23 ° C. for 8 minutes to achieve thermal parallelism before measurement. Specimens were compression molded according to ASTM D-4703-A Annex A at about 190 ° C. with an initial heating time of 5 minutes and a cooling rate of 15 ° C./minute for Procedure C. The test piece was cooled to 45 ° C. with a compressor, and the cooling was continued until it became “cool enough to be touched by hand”.

The melt index (I ₂ ) was measured at 190 ° C. under a load of 2.16 kg according to ASTM D-1238-03.

The melt index (I ₅ ) was measured at 190 ° C. under a load of 5.0 kg according to ASTM D-1238-03.

The melt index (I ₁₀ ) was measured at 190 ° C. under a load of 10.0 kg according to ASTM D-1238-03.

The melt index (I _21.6 ) was measured at 190 ° C. under a load of _21.6 kg according to ASTM D-1238-03.

The weight average molecular weight (M _w ) and number average molecular weight (M _n ) were determined according to methods known in the art using conventional GPC as described herein below.

The molecular weight distribution of the ethylene-based polymer was determined by gel permeation chromatography (GPC). The chromatographic apparatus consisted of a Waters (Millford, Mass.) 150 ° C. high temperature gel permeation chromatograph equipped with a Precision Detectors (Amherst, Mass.) 2-angle laser light scattering detector model 2040. A 15 ° angle light scattering detector was used for the calculations. Data collection was performed using Viscotek TriSEC software version 3 and a 4-channel Viscotek Data Manager DM400. The system was equipped with an on-line solvent degas device manufactured by Polymer Laboratories. The carousel compartment was operated at 140 ° C and the column compartment was operated at 150 ° C. The columns used were four Shodex HT 806M 300 mm, 13 μm columns and one Shodex HT803M 150 mm, 12 μm column. The solvent used was 1,2,4 trichlorobenzene. Samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatography solvent and sample preparation solvent contained 200 μg / g butylated hydroxytoluene (BHT). Both solvent sources were sparged with nitrogen. The polyethylene sample was gently stirred at 160 ° C. for 4 hours. The injection volume used was 200 microliters and the flow rate was 0.67 milliliters / minute. Calibration of the GPC column set consists of six “cocktails” that separate 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 g / mol into at least 10 individual molecular weights. This was carried out using the mixture. Standards were purchased from Polymer Laboratories (Shropshire, UK). A polystyrene standard is prepared to 0.025 grams in 50 milliliters of solvent for molecular weights greater than 1,000,000 g / mol, and in 50 milliliters of solvent for molecular weights less than 1,000,000 g / mol. Prepared to 0.05 grams. The polystyrene standard product was dissolved for 30 minutes at 80 ° C. while slowly stirring. A narrow standard mixture was run first and in decreasing order of highest molecular weight components to minimize degradation. Polystyrene standard peak molecular weight is calculated using the following equation (Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):
Mpolyethylene = Ax (Mpolystyrene) ^B
(Wherein M is molecular weight, A is a value of 0.41 and B is equal to 1.0). A systematic approach to the determination of multi-detector offsets is the method of Bulk, Balke, Chromatography Polym. Chpt 12, (1992) and Balke, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, ( 1992)), and the dual detector log results from Dow's wide polystyrene 1683 were compared to narrow standard column calibration results from narrow standard calibration curves using in-house software. Optimized. Molecular weight data for offset determination are available from Jim (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratovvil (P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY ( 1987)) was obtained in a manner consistent with that published by. The total injection concentration used to determine the molecular weight was measured from a linear polyethylene homopolymer with a molecular weight of 115,000 g / mol according to NIST polyethylene homopolymer standard 1475, sample refractive index area and refractive index detector calibration. (The sample refractive index area and the refractive index detector calibration). The chromatographic concentration was considered low enough to eliminate the coping with the second virial coefficient effect (concentration effect on molecular weight). Molecular weight calculations were performed using in-house software. Number average molecular weight, weight average molecular weight, and z average molecular weight calculations were performed according to the following equations, assuming that the refractometer signal was directly proportional to the weight fraction. The refractometer signal with reduced baseline can be directly replaced by weight fraction in the equation below. Note that the molecular weight can be an absolute molecular weight obtained from light scattering versus a conventional calibration curve or refractometer ratio. An improved estimate of the z-average molecular weight, the light scattering signal minus the baseline, can replace the product of the weight average molecular weight and weight fraction in equation (2) below.

  Bimodal distributions are described, for example, in Wild et al., Journal of Polymer Science, Poly. Phys. Ed., Vol. 20, p. 441 (1982), the entire disclosure of which is incorporated herein by reference. Temperature programmed elution fractionation (generally abbreviated as “TREF”) as described in US Pat. No. 4,798,081 (Hazlitt et al.) Or US Pat. No. 5,089,321 (Chum et al.). Characterized) according to the weight fraction of the maximum temperature peak of the data. In analytical temperature rising elution fractional analysis (described in US Pat. No. 4,798,081, herein abbreviated “ATREF”), the composition to be analyzed is subjected to a suitable thermal solvent (eg, 1, 2,4 trichlorobenzene) and crystallized by gradually lowering the temperature in a column containing an inert carrier (eg, stainless steel shot). The column was equipped with an infrared detector and a differential viscometer (DV) detector. Next, an ATREF-DV chromatogram curve was prepared by eluting the polymer sample crystallized by gradually increasing the temperature of the elution solvent (1,2,4 trichlorobenzene) from the column. The ATREF-DV method is described in further detail in WO 99/14271, the disclosure of which is hereby incorporated by reference.

  The high-density fraction (percent) is determined by analytical temperature programmed elution fractionation analysis (described in US Pat. No. 4,798,081 and abbreviated herein as “ATREF”), described in more detail below. It was measured. Analytical temperature-programmed elution fractionation (ATREF) analysis is described in US Pat. No. 4,798,081, which is incorporated herein in its entirety. Lisle, T .; R. Novelloch, D .; C. Pete, I .; R. Determination of Branching Distributions in Polyethylene and Ethylene Copolymers, J. Polym. Sci, 20, 441-455 (1982). Crystallization by dissolving the composition to be analyzed in trichlorobenzene and gradually lowering the temperature to 20 ° C. at a cooling rate of 0.1 ° C./min in a column containing an inert carrier (eg stainless steel shot). Make it. The column was equipped with an infrared detector. Next, an ATREF chromatogram curve was prepared by eluting the polymer sample crystallized by gradually increasing the temperature of the elution solvent (trichlorobenzene) from 20 to 120 ° C. at a rate of 1.5 ° C./min.

  Branch distribution was determined by crystallization analysis fractionation (CRYSTAF) (described herein below). Crystallization analysis fractionation (CRYSTAF) was performed with a CRYSTAF 200 unit commercially available from PolymerChar, Valencia, Spain. The sample was dissolved in 1,2,4 trichlorobenzene at 160 ° C. (0.66 mg / mL) for 1 hour and stabilized at 95 ° C. for 45 minutes. The sampling temperature was in the range of 95-30 ° C. with a cooling rate of 0.2 ° C./min. The polymer solution concentration was measured using an infrared detector. The cumulative soluble concentration was measured as the polymer crystallized as the temperature decreased. The analytical derivative of the cumulative profile reflects the short chain branching distribution of the polymer.

  CRYSTAF temperature peaks and areas are identified by the peak analysis module included in the CRYSTAF software (Version 2001.b, PolymerChar, Valencia, Spain). The CRYSTAF peak finding routine identifies the temperature peak as the area between the maximum value of the dW / dT curve and the largest positive inflections on either side of the peak identified in the derivative curve. Preferred processing parameters for calculating the CRYSTAF curve have a temperature limit of 70 ° C. and smoothing parameters above the temperature limit of 0.1 and below the temperature limit of 0.3.

（式中、Ｔは温度であり、Ｗは重量分率であり、Ｔ_wは重量平均温度である）
に基づいて計算されるＣＲＹＳＴＡＦ法の幅に関する統計値である。 The solubility distribution width index (SDBI) is

(Where T is the temperature, W is the weight fraction, and T _w is the weight average temperature)
Is a statistical value related to the width of the CRYSTAF method calculated based on

  Long chain branching is performed by methods known in the art, such as gel permeation chromatography in combination with a low angle light scattering detector (GPC-LALLS) and gel permeation chromatography in combination with a differential viscometer detector (GPC-DV). Measured according to

  Resin stiffness is measured according to ASTM D790-99 Method B, flexural modulus at 5 percent strain and secant modulus at 1 percent and 2 percent strain, and test speed of 0.5 inch / min (13 mm / min). It was characterized by

  Yield tensile strength and elongation at break were measured according to ASTM D-638-03 using a 2 inch / min (50 mm / min) type IV specimen.

Environmental stress crack resistance (ESCR) was measured according to ASTM D1693-01, Condition B. Resin sensitivity to mechanical failure due to cracks was measured in the presence of crack accelerators such as soaps, wetting agents, etc. under constant strain conditions. Measurements were made in 10 weight percent Igepal CO-630 (Rhone-Poulec, NJ sales) aqueous solution maintained at 50 ° C. and 100 weight percent Igepal CO-630 (Rhone-Poulec, NJ sales) maintained at 50 ° C. ) It was performed with a notched specimen in an aqueous solution. The ESCR values were reported as F ₅₀ , which is the calculated 50 percent failure time calculated from the probability graph, and F ₀ without failure during the test.

The short chain branching distribution and comonomer content are described in Randall, Rev. Macromol. Chem. Chys., C29 (2 & 3), pp. 285-297, the disclosure of which is hereby incorporated by reference to the extent that such disclosure relates to such measurements. , And C ₁₃ NMR discussed in US Pat. No. 5,292,845. Samples were prepared by adding approximately 3 g of a 50/50 mixture of tetrachloroethane-d2 / orthodichlorobenzene, which was 0.025 M in chromium acetylacetonate (relaxation agent), to a 0.4 g sample in a 10 mm NMR tube. did. The sample was dissolved and homogenized by heating the tube and its contents to 150 ° C. Data was collected using a JEOL Eclipse 400 MHz NMR spectrometer, corresponding to a 13C resonance frequency of 100.6 MHz. Acquisition parameters were selected to ensure quantitative 13C data acquisition in the presence of a relaxation agent. Data is a file of gate 1H decoupling, 4000 transients per data file, 4.7 second relaxation delay and 1.3 second acquisition time, 24,200 Hz spectral width and 64K data points. Using the size, the detection head was acquired by heating to 130 ° C. The spectrum was contrasted with a 30 ppm methylene peak. Results were calculated according to ASTM method D5017-91.

Resin rheology was measured with an ARES I (Advanced Rheometric Expansion System) rheometer. ARES I was a strain controlled rheometer. The rotary actuator (servomotor) was adapted to shear strain in the form of strain on the sample. In response, the sample developed a torque that was measured by the transducer. Strain and torque were used to calculate dynamic mechanical properties such as modulus and viscosity. The viscoelastic properties of the samples are variable frequency (0.01-500 s ⁻¹ ) in the melt using 25 mm diameter parallel plates set to constant strain (5 percent) and temperature (190 ° C.) and N ₂ purge. ) As a function. The storage modulus, loss modulus, tan delta, and complex viscosity of the resin were determined using Rheometrics Orchestrator software (v. 6.5.8). The viscosity ratio (0.1 rad ^* s ⁻¹ / 100 rad ^* s ⁻¹ ) was determined as the ratio of the viscosity measured at a shear rate of 0.1 rad / s to the viscosity measured at a shear rate of 100 rad / s.

  Vinyl unsaturation was measured according to ASTM D-6248-98.

  Low shear rheological characterization is performed in a stress controlled mode Rheometrics SR5000 using a 25 mm parallel plate fixture. This type of shape is preferably cones and planes that require minimal squeeze flow during sample loading and thus reduce residual stress.

  The g 'average was determined according to the following procedure. The chromatographic apparatus is a Waters (Millford, MA) 150 ° C. high temperature gel permeation equipped with Precision Detectors (Amherst, MA) two-angle laser light scattering detector model 2040 and an IR4 infrared detector from Polymer Char (Valencia, Spain) Chromatograph and Viscotek (Houston, TX) 150R 4-capillary viscometer. A 15 ° angle light scattering detector was used for the calculations. Data collection was performed using Viscotek TriSEC software version 3 and a 4-channel Viscotek Data Manager DM400. The system was equipped with an on-line solvent degasser from Polymer Laboratories. The carousel compartment was operated at 140 ° C and the column compartment was operated at 150 ° C. The columns used were four 20-micron mixed-bed light scattering “Mixed A-LS” columns from Polymer Laboratories. The solvent used was 1,2,4 trichlorobenzene. Samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatography solvent and sample preparation solvent contained 200 ppm butylated hydroxytoluene (BHT). Both solvent sources were sparged with nitrogen. The polyethylene sample was gently stirred at 160 ° C. for 4 hours. The injection volume used was 200 microliters and the flow rate was 1 milliliter / minute.

Calibration of the GPC column set consists of six “cocktail” mixtures separating 21 narrow molecular weight distribution polystyrene standards with molecular weights ranging from 580 to 8,400,000 into at least 10 individual molecular weights. It was performed using what was done. Standards were purchased from Polymer Laboratories (Shropshire, UK). A polystyrene standard is prepared to 0.025 grams in 50 milliliters of solvent for molecular weights greater than 1,000,000 and 0.05 grams in 50 milliliters of solvent for molecular weights less than 1,000,000. Prepared. The polystyrene standard product was dissolved for 30 minutes at 80 ° C. while slowly stirring. A narrow standard mixture was run first and in decreasing order of highest molecular weight components to minimize degradation. Polystyrene standard peak molecular weight is calculated using the following equation (Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):
Mpolyethylene = Ax (Mpolystyrene) ^B
(Wherein M is the molecular weight, A is a value of 0.43, and B is equal to 1.0).

  A systematic approach for the determination of multi-detector offsets is described by Bale, Thitiratsakul, Lew, Cheung, Mourey, Chromatography Polym. Chpt 13, Chloetography, Polym. Chpt 12, (1992). (1992)), and the triple detector log (MW and IV) results from Dow Broad polystyrene 1683 were converted into narrow standard column calibration results from narrow standard calibration curves using software. Optimized for. Molecular weight data for offset determination are available from Jim (Zimm, BH, J. Chem. Phys., 16, 1099 (1948)) and Kratovvil (P., Classical Light Scattering from Polymer Solutions, Elsevier, Oxford, NY ( 1987))). The total injection concentration used to determine the molecular weight was obtained from the sample refractive index area and refractive index detector calibration from a linear polyethylene homopolymer of 115,000 molecular weight. The chromatographic concentration was considered low enough to eliminate the coping with the second virial coefficient effect (concentration effect on molecular weight).

The g ′ average was calculated for the sample as follows.
1. Light scattering, viscosity, and concentration detectors were calibrated with NBS 1475 homopolymer polyethylene (or equivalent control);
2. Light scattering and viscometer detector offsets were corrected as described in the calibration section for the concentration detector;
3. Subtract baseline from light scatter, viscometer, and concentration chromatograms, set integration window to ensure integration of all low molecular weight retention dose ranges in light scatter chromatograms observable from refractometer chromatograms;
4). A linear homopolymer polyethylene Mark-Houwink baseline is established by injecting a standard with a polydispersity of at least 3.0, a data file (obtained from the above calibration method) is calculated, and each chromatographic slice The intrinsic viscosity and molecular weight from the mass constant correction data for was recorded;
5. Injecting the HDPE sample of interest, calculating a data file (obtained from the above calibration method) and recording the intrinsic viscosity and molecular weight from the mass constant correction data for each chromatographic slice;
6). The intrinsic viscosity of the homopolymer linear control is determined by the following factors: IV = IV + 1 / (1 + 2 ^* SCB / 1,000C ^* branch point length), where IV is the intrinsic viscosity of the HDPE sample of interest and SCB / 1,000 C was determined from C13 NMR and the branch point length was 2 for butene, 4 for hexene and 6 for octene);
7). The g ′ average was calculated according to the following equation:

式中、ｃはスライスの濃度であり、ＩＶはＨＤＰＥの固有粘度であり、ＩＶ_Lは線状ホモポリマーポリエチレン対照（関心対象のＨＤＰＥ試料のＳＣＢについて補正）の同じ分子量（Ｍ）での固有粘度である。ＩＶ比は、光散乱データ中の自然の散乱を説明する４０，０００未満の分子量でのものであると考えた。

Where c is the slice concentration, IV is the HDPE intrinsic viscosity, and IV _L is the intrinsic viscosity at the same molecular weight (M) of the linear homopolymer polyethylene control (corrected for the SCB of the HDPE sample of interest). It is. The IV ratio was considered to be at a molecular weight of less than 40,000, which explains the natural scattering in the light scattering data.

  The present invention may be embodied in other forms without departing from its spirit and essential characteristics, and therefore, refer to the appended claims rather than the foregoing specification as indicating the scope of the invention. I want to be.

It is a graph explaining the relationship between the comonomer content and density of the high-density polyethylene composition of this invention. 6 is a graph illustrating the relationship between high density fraction and density as measured by analytical temperature programmed elution fractionation analysis (ATREF) of the high density polyethylene composition of the present invention. FIG. 3 is a graph illustrating the relationship between the calculated high density fraction and the density, as measured by analytical temperature rising elution fractionation analysis (ATREF), of the high molecular weight polyethylene component of the high density polyethylene composition of the present invention. is there. 2 is a graph showing how the calculated ATREF high density fraction of the high molecular weight polyethylene component of Example 1 of the present invention was determined.

Claims (41)

Comprising a first component, wherein the first component has a density in the range of 0.915 to 0.940 g / cm ³ and a melt index (I _21.6 ) in the range of 0.5 to 10 g / 10 min. A high molecular weight ethylene α-olefin copolymer having a second component, the second component having a density in the range of 0.965 to 0.980 g / cm ³ , and 50 to 1500 g / 10 min. A high density polyethylene composition that is a low molecular weight ethylene polymer having a melt index (I ₂ ) in the range of;
The high-density polyethylene composition has a melt index (I ₂ ) of at least 1 g / 10 min, a density in the range of 0.950 to 0.960 g / cm ³ , a g 'of 1 or more, and a molecular weight distribution of 7 to 17 (Mw / Mn) and ASTM D-1693 Condition B, at least 150 hours measured by 10 percent Igepal, or ASTM D-1693 Condition B, environmental stress crack resistance measured by 100 percent Igepal for at least 300 hours A high density polyethylene composition comprising: The high density polyethylene composition of claim 1, wherein the first component has a density in the range of 0.920 to 0.940 g / cm ³ . The high density polyethylene composition of claim 1, wherein the first component has a density in the range of 0.921 to 0.936 g / cm ³ . The high-density polyethylene composition according to claim 1, wherein the first component has a melt index (I _21.6 ) in the range of 1 to 7 g / 10 minutes. The high density polyethylene composition of claim 1, wherein the first component has a melt index (I _21.6 ) in the range of 1.3 to 5 g / 10 min. The high density polyethylene composition of claim 1, wherein the second component has a density in the range of 0.970 to 0.975 g / cm ³ . The second component has a melt index _{(I 2)} in the range of 100 to 1500 g / 10 min, high-density polyethylene composition according to claim 1. The high-density polyethylene composition according to claim 1, wherein the second component has a melt index (I ₂ ) in the range of 200 to 1500 g / 10 minutes. The high density polyethylene composition according to claim 1, wherein the high density polyethylene composition has a melt index (I ₂ ) in the range of 1 to ₂ g / 10 minutes. The high density polyethylene composition of claim 1, wherein the high density polyethylene composition has a melt index (I ₂ ) of at least 2 g / 10 minutes.   The high density polyethylene composition of claim 1, wherein the first component has a molecular weight in the range of 150,000 to 375,000.   The high density polyethylene composition of claim 1, wherein the second component has a molecular weight in the range of 12,000 to 40,000. The first component has a density in the range of 0.921 to 0.936 g / cm ³ and a melt index (I _21.6 ) in the range of 1.3 to 5 g / 10 minutes; There has a melt index in the range of density, and 200~1500g / 10 min in the range of _{^{0.970~0.975g / cm 3 (I 2)}} , high-density polyethylene composition according to claim 1.   The first component is substituted with less than 0.1 long chain branches per 1000 total carbons, and the second component is replaced with less than 0.1 long chain branches per 1000 total carbons; The high-density polyethylene composition according to claim 1.   15. The high density polyethylene composition of claim 14, wherein the high density polyethylene composition is substituted with less than 0.1 long chain branches per 1000 total carbons. The high density polyethylene composition has a single ATREF temperature peak, the ATREF temperature peak having a temperature peak maximum between 90 ° C. and 105 ° C .;
The high density polyethylene composition has a calculated high density fraction in the range of 20 percent to 50 percent, and the calculated high density fraction is [(2) X (the temperature peak maximum in ATREF-DV Defined as the weight ratio of high density polyethylene eluting at the above temperature),
The high density polyethylene composition has a minimum value of a log of relative viscosity average molecular weight at 90 ° C. in ATREF-DV;
The high density polyethylene composition has a regression slope of a log of a relative viscosity average molecular weight of less than 0 versus ATREF-DV viscosity versus temperature, and the elution temperature is measured between 70 ° C and 90 ° C. The high-density polyethylene composition according to claim 1. The high-density polyethylene composition is [(−228.41 ^* density of the high-density polyethylene composition) +219.36)] ^* [1 (weight percent) / (g / cm ³ )] or more weight percent comonomer. The high-density polyethylene composition according to claim 1, having a content, the density of which is measured in g / cm ³ . The high density polyethylene composition has an ATREF high density fraction of [(2750 ^* density of the high density polyethylene composition) -2552.2] ^* [1 (percent) / (g / cm ³ )] or less. The high density polyethylene composition according to claim 1, wherein the density is measured in g / cm ³ . Introducing ethylene and an α-olefin comonomer into the first reactor;
Polymerizing said ethylene in the presence of said α-olefin comonomer in said first reactor, thereby producing a first component, wherein 0.915-0.940 g of said first component A high molecular weight ethylene α-olefin copolymer having a density in the range of / cm ³ and a melt index (I ₂₁ ) in the range of 0.5 to 10 g / 10 min;
Introducing said first component and further ethylene into a second reactor;
Polymerizing said further ethylene in said second reactor, thereby producing a second component, said second component having a density in the range of 0.965 to 0.980 g / cm ³ ; And a low molecular weight ethylene-based polymer having a melt index (I ₂ ) in the range of 50-1500 g / 10 min;
Thereby producing said high density polyethylene composition, wherein the high density polyethylene composition has a melt index (I ₂ ) of at least 1 g / 10 min, a density in the range of 0.950 to 0.960 g / cm ^3. 1 or more g ', 7 to 17 molecular weight distribution (Mw / Mn), and ASTM D-1693 Condition B, at least 150 hours as measured by 10 percent Igepal, or ASTM D-1693 Condition B, 100 percent And having an environmental stress crack resistance of at least 300 hours as measured by Igepal of the method. 20. The method for producing a high density polyethylene composition according to claim 19, wherein the first component has a density in the range of 0.920 to 0.940 g / cm < ³ >. 20. The method for producing a high density polyethylene composition according to claim 19, wherein the first component has a density in the range of 0.921 to 0.936 g / cm < ³ >. Wherein said first component having a melt index _{(I 21.6)} in the range of 1 to 7 g / 10 min, to produce a high-density polyethylene composition according to claim 19. Wherein said first component having a melt index _{(I 21.6)} in the range of 1.3~5g / 10 min, to produce a high-density polyethylene composition according to claim 19. 20. The method for producing a high density polyethylene composition according to claim 19, wherein the second component has a density in the range of 0.970 to 0.975 g / cm < ³ >. The method of the second component has a melt index _{(I 2)} in the range of 100 to 1500 g / 10 min, to produce a high-density polyethylene composition according to claim 19. The method of the second component has a melt index _{(I 2)} in the range of 200~1500g / 10 min, to produce a high-density polyethylene composition according to claim 19. Wherein said high-density polyethylene composition has a melt index (I ₂₎ in the range of 1 to 2 g / 10 min, to produce a high-density polyethylene composition according to claim 19. Wherein said high-density polyethylene composition has at least 2 g / 10 min melt index (I _2), to produce a high-density polyethylene composition according to claim 19.   20. The method for producing a high density polyethylene composition according to claim 19, wherein the first component has a molecular weight in the range of 150,000 to 375,000.   20. The method for producing a high density polyethylene composition according to claim 19, wherein the second component has a molecular weight in the range of 12,000 to 40,000. The first component has a density in the range of 0.921 to 0.936 g / cm ³ and a melt index (I _21.6 ) in the range of 1.3 to 5 g / 10 minutes; method but having a melt index in the range of density, and 200~1500g / 10 min in the range of _{^{0.970~0.975g / cm 3 (I 2)}} , to produce a high-density polyethylene composition according to claim 19 .   The first component is substituted with less than 0.1 long chain branches per 1000 total carbons and the second component is replaced with less than 0.1 long chain branches per 1000 total carbons A method for producing the high-density polyethylene composition according to claim 19.   35. The method of making a high density polyethylene composition according to claim 32, wherein the high density polyethylene composition is substituted with less than 0.1 long chain branches per 1000 total carbons. The high density polyethylene composition has a single ATREF temperature peak, the ATREF temperature peak having a temperature peak maximum between 90 ° C. and 105 ° C .;
The high density polyethylene composition has a calculated high density fraction in the range of 20 percent to 50 percent, and the calculated high density fraction is [(2) ^* (the temperature peak maximum in ATREF-DV Defined as the weight ratio of high density polyethylene eluting at the above temperature),
The high density polyethylene composition has a minimal value of log of relative viscosity average molecular weight at 90 ° C. in ATREF-DV;
The high density polyethylene composition has a log regression analysis slope of a plot of relative viscosity average molecular weight of less than 0 versus ATREF-DV viscosity versus temperature, and the elution temperature is measured between 70 ° C and 90 ° C. Item 20. A method for producing the high-density polyethylene composition according to Item 19. The high-density polyethylene composition is [(−228.41 ^* density of the high-density polyethylene composition) +219.36)] ^* [1 (weight percent) / (g / cm ³ )] or more weight percent comonomer. 20. A method for producing a high density polyethylene composition according to claim 19 having a content, the density of which is measured in g / cm < ³ >. The high density polyethylene composition has an ATREF high density fraction of [(2750 ^* density of the high density polyethylene composition) -2552.2] ^* [1 (percent) / (g / cm ³ )] or less. The method for producing a high-density polyethylene composition according to claim 19, wherein the density is measured in g / cm ³ . A first component having a density in the range of 0.915 to 0.940 g / cm ³ and a melt index (I _21.6 ) in the range of 0.5 to 10 g / 10 min. A high molecular weight ethylene α-olefin copolymer; and comprising a second component, wherein the second component has a density in the range of 0.965 to 0.980 g / cm ³ , and a range of 50 to 1500 g / 10 min. A low molecular weight ethylene polymer having a melt index (I ₂ ) of
A high density polyethylene composition,
The high-density polyethylene composition has a melt index (I ₂ ) of at least 1 g / 10 min, a density in the range of 0.950 to 0.960 g / cm ³ , a g 'of 1 or more, and a molecular weight distribution of 7 to 17 (Mw / Mn) and ASTM D-1693 Condition B, at least 150 hours measured by 10 percent Igepal, or ASTM D-1693 Condition B, environmental stress crack resistance measured by 100 percent Igepal for at least 300 hours Have a product.   38. The product of claim 37, wherein the product is a wire cable jacket, conduit, or injection blow molded bottle. A first component having a density in the range of 0.915 to 0.940 g / cm ³ and a melt index (I _21.6 ) in the range of 0.5 to 10 g / 10 min. A high molecular weight ethylene α-olefin copolymer; and comprising a second component, wherein the second component has a density in the range of 0.965 to 0.980 g / cm ³ , and a range of 200 to 1500 g / 10 min. A low molecular weight ethylene polymer having a melt index (I ₂ ) of
A high density polyethylene composition,
The high-density polyethylene composition has a melt index (I ₂ ) of at least 1 g / 10 min, a density in the range of 0.950 to 0.960 g / cm ³ , a g 'of 1 or more, and a molecular weight distribution of 7 to 17 (Mw / Mn) and ASTM D-1693 Condition B, at least 150 hours measured by 10 percent Igepal, or ASTM D-1693 Condition B, environmental stress crack resistance measured by 100 percent Igepal for at least 300 hours Has a bottle cap closure. A first component having a density in the range of 0.915 to 0.940 g / cm ³ and a melt index (I _21.6 ) in the range of 0.5 to 10 g / 10 min. A high molecular weight ethylene α-olefin copolymer; and comprising a second component, wherein the second component has a density in the range of 0.965 to 0.980 g / cm ³ , and a range of 50 to 1500 g / 10 min. A low molecular weight ethylene polymer having a melt index (I ₂ ) of
Providing a high density polyethylene composition comprising:
The high density polyethylene composition has a melt index (I ₂ ) of at least 1 g / 10 min, a density in the range of 0.950 to 0.960 g / cm ³ , a g 'of 1 or more, and a molecular weight distribution of 7 to 17 (Mw / Mn) and ASTM D-1693 Condition B, at least 150 hours measured by 10 percent Igepal, or ASTM D-1693 Condition B, environmental stress crack resistance measured by 100 percent Igepal for at least 300 hours A stage to have;
Compression-molding, blow-molding, or injection-molding the high-density polyethylene composition, thereby forming an improved bottle cap closure. A first component having a density in the range of 0.915 to 0.940 g / cm ³ and a melt index (I _21.6 ) in the range of 0.5 to 10 g / 10 min. A high molecular weight ethylene α-olefin copolymer; and comprising a second component, wherein the second component has a density in the range of 0.965 to 0.980 g / cm ³ , and a range of 50 to 1500 g / 10 min. A low molecular weight ethylene polymer having a melt index (I ₂ ) of
Providing a high density polyethylene composition comprising:
The high density polyethylene composition has a melt index (I ₂ ) of at least 1 g / 10 min, a density in the range of 0.950 to 0.960 g / cm ³ , a g 'of 1 or more, and a molecular weight distribution of 7 to 17 (Mw / Mn) and ASTM D-1693 Condition B, at least 150 hours measured by 10 percent Igepal, or ASTM D-1693 Condition B, environmental stress crack resistance measured by 100 percent Igepal for at least 300 hours A stage to have;
Compression molding, blow molding, or injection molding the high density polyethylene composition, thereby forming the product.

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